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Giant negative thermal expansion in ultrafine-grained Mn3(Cu1−x Gex )N (x = 0.5) bulk

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2009 J. Phys. D: Appl. Phys. 42 122004

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IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 42 (2009) 122004 (5pp) doi:10.1088/0022-3727/42/12/122004

FAST TRACK COMMUNICATION

Giant negative thermal expansion in

ultrafine-grained Mn3(Cu1−xGex)N
(x = 0.5) bulk
Z H Sun1 , X Y Song1 , F X Yin2 , L X Sun3 , X K Yuan1 and X M Liu1
1
College of Materials Science and Engineering, Key Laboratory of Advanced Functional Materials,
Chinese Education Ministry, Beijing University of Technology, Beijing 100124, People’s Republic of
China
2
Innovative Materials Engineering Laboratory, National Institute for Materials Science, Tsukuba,
Ibaraki 305-0047, Japan
3
Material and Thermochemistry Laboratory, Dalian Institute of Chemical Physics, Chinese Academy of
Sciences, Dalian 116023, People’s Republic of China
E-mail: xysong@bjut.edu.cn

Received 15 April 2009

Published 29 May 2009
Online at stacks.iop.org/JPhysD/42/122004

Abstract
The advanced negative thermal expansion (NTE) properties of the ultrafine-grained
Mn3 (Cu1−x Gex )N compound bulk have been reported. The developed preparation route has
reduced the fabrication time by more than ten times in contrast to previous studies. As
compared with the coarse-grained compound bulk, the NTE start temperature of the ultrafine
Mn3 (Cu1−x Gex )N (x = 0.5) bulk is reduced to 250 K, and the coefficient of negative thermal
expansion (CNTE) reaches −23.7 × 10−6 K−1 , which is remarkably improved. It is found that
the nitrogen content in the starting manganese nitride also has significant effects on the NTE
start temperature, operating temperature range and CNTE.
(Some figures in this article are in colour only in the electronic version)

As a particular type of functional materials, negative thermal
expansion (NTE) materials can be used to compensate or
control the conventional (positive) thermal expansion by means
of forming zero thermal expansion composites, which have
the potential for wide application in the fields of high-
precision optical mirrors, refractive index gratings, printed
circuit boards, heat sinks, etc [1]. The recent discoveries of
excellent NTE properties in antiperovskite-structured Mn3 AN
(A = Cu, Zn, etc) doped with Ge, Sn or Ga [2–4] have
attracted considerable interest. These kinds of compounds
have the advantages of being uniquely metallic, isotropic,
having adjustable coefficient of NTE (CNTE) and operating
temperature range (
T ) [2, 3] in comparison with the known
NTE materials.
Among the Mn3 CuN-based NTE materials, the Ge-doped
Mn3 CuN compounds exhibit the best NTE property that has
been reported in the literature so far [2, 3, 5]. The Ge-doped
Mn3 CuN compounds reveal the NTE property around room
temperature. With the increase in Ge addition, the Néel
temperature and the NTE operation temperature range of this
compound increase, while the absolute value of CNTE and the
magnetization decrease. To obtain the low-temperature NTE
property, as well as the broader NTE operation temperature
range, Huang et al attempted to substitute Ge with Nb
and Si in Mn3 (Cu1−x Gex N) (x = 0.4) [6, 7]. However,
even with the maximum addition of Nb as 0.2 at%, the
absolute CNTE of the compound had a fairly low value of
5 × 10−6 K−1 . It is worth noting that to achieve the low-
temperature NTE, the broad NTE operation temperature range
and the large CNTE value, the method of Ge substitution
is limited by the type and the content of the doping
elements.

0022-3727/09/122004+05$30.00 1 © 2009 IOP Publishing Ltd Printed in the UK

J. Phys. D: Appl. Phys. 42 (2009) 122004
In this work, we report a novel approach to achieve
the low-temperature NTE, the large CNTE and the broad
NTE operation temperature range of the Ge-doped Mn3 CuN
compounds. A new simple method was developed to prepare
the ultrafine-grained Mn3 (Cu1−x Gex )N (x = 0.5) compound
bulk by combining the synthesis of the amorphous powder with
densification by the spark plasma sintering (SPS) technique.
We focus on the effects of the grain size on the low-temperature
NTE behaviour and investigate the influences of nitrogen
content on the NTE properties of the Mn3 (Cu1−x Gex )N
compounds.
The composition of Mn3 (Cu1−x Gex )N (x = 0.5) was
selected in our experimental work, due to the report [2] that
the Mn3 (Cu0.5 Ge0.5 )N had a continuous NTE behaviour and
a relatively wide NTE operation temperature range among
the Mn3 (Cu1−x Gex )N compounds. Pure Mn (99.95%), Cu
(99.5%) and Ge (99.999%) powders with a mean particle
size of ∼45 µm and pure N2 gas (99.999%) were used as
the starting materials. Firstly, the single-phase Mn2 N0.86
powder was synthesized by the solid–gas reaction of Mn
particles and N2 gas in the vacuum furnace at 1023 K for 5 h.
Then, the Cu and Ge powders with masses calculated from
the stoichiometric content of Mn3 (Cu0.5 Ge0.5 )N were mixed
with the Mn2 N0.86 powder by ball milling. The amorphous
Mn3 (Cu0.5 Ge0.5 )N powder was obtained after high-energy ball
milling with a ball-to-powder weight ratio of 10 : 1 at a rotation
speed of 450 rpm for 20 h. Subsequently, the amorphous
compound powder was sintered by the SPS technique; in
the process the powder structure evolved in the sequence of
crystallization and densification. For the sintering procedure,
a heating rate of 100 K min−1 was used till the final sintering
temperature of 1093 K. An external pressure of 60 MPa was
applied to the powder in the temperature range from 1033 to
1093 K. At the sintering temperature the sample was held for
10 min.
The ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N compound bulk
was prepared by the above route. For comparison, the coarse-
grained Mn3 (Cu0.5 Ge0.5 )N compound bulk was prepared by
SPS densification using the Mn2 N0.86 , Cu and Ge powders as
the sintering materials, which have a polycrystalline structure
due to the absence of the high-energy ball milling. Both the
SPS processes were performed under nitrogen atmosphere to
inhibit the nitrogen loss of manganese nitride.
The variations of the lattice constants with temperature
were characterized by x-ray diffraction (XRD, D8 Discovery)
with general area detector diffraction solution (GADDS).
The magnetic properties of the prepared bulk samples were
measured by a superconducting quantum-interference device
(SQUID) magnetometer in a temperature range from 400 K
down to 10 K with an external field of 500 Oe.
The phase analyses on the prepared Mn2 N0.86 and
amorphous Mn3 (Cu0.5 Ge0.5 )N powders, as well as the
Mn3 (Cu0.5 Ge0.5 )N bulks with coarse- and ultrafine-grained
structures, are shown in figure 1 by XRD patterns
corresponding to the different preparation stages. The
synthesized Mn2 N0.86 powder has a single phase with
the hexagonal crystal structure (space group P 63 22), as
analysed from the XRD pattern in figure 1(a). The lattice
2
Fast Track Communication
Figure 1. XRD patterns of samples at different preparation stages:
(a) the Mn2 N0.86 powder synthesized by solid–gas reaction, (b) the
amorphous Mn3 (Cu0.5 Ge0.5 )N powder obtained by high-energy ball
milling, (c) the Mn3 (Cu0.5 Ge0.5 )N bulk prepared by SPS of the
amorphous powder and (d) the Mn3 (Cu0.5 Ge0.5 )N bulk prepared by
SPS of the Mn2 N0.86 , Cu and Ge powders.
constants were calculated as a = 4.818 Å and c =
4.526 Å from the XRD data. The amorphous structure
of the Mn3 (Cu0.5 Ge0.5 )N powder obtained by high-energy
ball milling is indicated by curve (b) in figure 1. The
XRD pattern of the Mn3 (Cu0.5 Ge0.5 )N bulk prepared by
crystallization and densification of the amorphous powder in
the SPS process is exhibited in figure 1(c). Correspondingly,
the microstructure of this compound bulk is shown in figure 2.
It can be observed that the prepared Mn3 (Cu0.5 Ge0.5 )N bulk
has an ultrafine-grain structure with the mean grain size of
approximately 300 nm. Figure 1(d) shows the XRD pattern of
the Mn3 (Cu0.5 Ge0.5 )N bulk prepared by SPS densification of
the mixture of the synthesized Mn2 N0.86 powder and the raw
Cu and Ge powders. The Mn3 (Cu0.5 Ge0.5 )N compound bulks
have the antiperovskite crystal structure (space group Pm3m),
as analysed from the XRD patterns.
The NTE properties were characterized by measurements
on the variations of the lattice constant with temperature, as
the results shown in figure 3. The NTE characteristics of the
prepared ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N compound bulk
show that the NTE operation temperature range is
T = 65 K
(187–252 K) and the CNTE is α = −23.7 × 10−6 K−1 . As a
comparison, the coarse-grained compound bulk has the NTE
operation temperature range as
T = 80 K (240–320 K) and
the CNTE as α = −16 × 10−6 K−1 . The ultrafine-grained
Mn3 (Cu0.5 Ge0.5 )N bulk exhibits much larger CNTE than that
of the coarse-grained bulk (see figure 3), which is about
twice over the value of the coarse-grained Mn3 (Cu0.5 Ge0.5 )N
compound reported by Takenaka and Takagi [2]. It has been
reported that the large thermal expansion coefficient of the
nanocrystalline materials results from the interface volume
expansion [8]. Although the direct evidence for the increase
in CNTE with the reduction in the grain size is lacking at
present, we believe that the remarkably increased fraction
of the interfaces in the ultrafine-grained Mn3 (Cu1−x Gex )N
J. Phys. D: Appl. Phys. 42 (2009) 122004
Figure 2. The transmission electron microscopy image of the
ultrafine-grain structure of the Mn3 (Cu0.5 Ge0.5 )N compound bulk
prepared by SPS of the amorphous powder.
Figure 3. Variations of the lattice constants with temperature of
coarse-grained and ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N bulks.
compound, as compared with the coarse-grained counterpart,
produces significant effects on the improvement of CNTE.
It is also found from figure 3 that the NTE start temperature
of the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N compound bulk is
252 K, which is reduced by approximately 70 K from that
of the coarse-grained bulk (320 K). It was acknowledged
that the NTE start temperature of the antiferromagnetic
Mn3 (Cu1−x Gex )N compounds corresponded to the magnetic
transition point, i.e. the Néel temperature [3, 5–7], which was
attributed to the magnetovolume effect [9]. As indicated by
the magnetization curve in figure 4(a), the Néel temperature
of the coarse-grained Mn3 (Cu0.5 Ge0.5 )N bulk is 316 K, which
is consistent with the NTE start temperature obtained from
figure 3, whereas this corresponding relationship does not exist
in the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N bulk. As shown by
the magnetization curve in figure 4(b), the ultrafine-grained
Mn3 (Cu0.5 Ge0.5 )N compound bulk has a ferromagnetic
3
Fast Track Communication
Figure 4. Temperature dependence of magnetization of (a) the
coarse-grained Mn3 (Cu0.5 Ge0.5 )N bulk and (b) the ultrafine-grained
Mn3 (Cu0.5 Ge0.5 )N bulk with an external field of 500 Oe.
characteristic below 107 K and a paramagnetic characteristic
above this temperature. Thus, there is no magnetic transition
point (the Néel temperature) corresponding to the NTE
start temperature of the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N
compound bulk. It is discovered by the present authors
that the NTE performance takes place in the range of the
paramagnetism of the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N
compound bulk. Very recently, Zheng et al reported that
CuO nanoparticles exhibited NTE properties [10], and the
NTE start temperature did not correspond to the Néel
temperature of CuO [11]. Moreover, it was shown that the
NTE behaviour occurred in the paramagnetism region of the
material. This phenomenon agrees well with our finding for
the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N compound bulk. We
consider that the NTE behaviour of the ultrafine- or nano-
scale materials cannot be explained by the magnetovolume
effect. Instead, the impact of the size scale on the NTE
properties should be caused by the magneto-lattice effect
[12]. The characteristics of the temperature dependence of the
lattice constants of the Mn3 (Cu1−x Gex )N compounds suggest
that magnetostriction plays a significant role in the NTE
behaviour. When the temperature is cooled down below the
magnetic ordering temperature, the lattice expansion induced
J. Phys. D: Appl. Phys. 42 (2009) 122004
and Takagi [2]
Figure 5. Comparison of NTE properties of the coarse-grained
Mn3 (Cu0.5 Ge0.5 )N compounds prepared using (a) Mn2 N [2],
(b) Mn2 N0.86 and (c) Mn4 N [5] as the starting materials. Inset: the
antiperovskite Mn3 CuN-type structure.
by magnetic ordering is larger than the lattice contraction
caused by the reduction of the temperature, leading to the
NTE performance. For the ultrafine-grained compound
bulk, the magnetostriction effect is greatly enhanced below
the magnetic ordering temperature due to the grain-size
effect. Consequently, the NTE performance of the ultrafine-
grained Mn3 (Cu0.5 Ge0.5 )N bulk occurs in the paramagnetism
region.
As introduced in the experimental procedures, both the
coarse- and the ultrafine-grained Mn3 (Cu0.5 Ge0.5 )N compound
bulks were prepared using Mn2 N0.86 powder as the starting
material, in contrast to most of the previous investigations
which used Mn2 N powder as the starting material to fabricate
the Mn3 (Cu1−x Gex )N compounds [2, 4, 6, 7]. It is worthwhile
to discuss the effects of nitrogen content in manganese nitrides
on the NTE behaviour of the resultant Mn3 (Cu1−x Gex )N
compounds.
It is found that the NTE start temperature of the
Mn3 (Cu0.5 Ge0.5 )N compound was reduced to 320 K in this
work from 365 K, as reported by Takenaka and Takagi [2],
when Mn2 N0.86 instead of Mn2 N was used as the starting
powder. Since the NTE start temperature is consistent with
the Néel temperature of antiperovskite Mn3 (Cu1−x Gex )N
compounds, the decrease in nitrogen content from Mn2 N to
Mn2 N0.86 should be responsible for the reduction in the Néel
temperature. This point of view has been identified by a very
new study by Zhang et al [5] that the Néel temperature of
Mn3 (Cu1−x Gex )N (x = 0.5) prepared using Mn4 N as the
starting material was as low as 250 K.
Moreover, the nitrogen content affects the NTE operation
temperature range and the CNTE of Mn3 (Cu1−x Gex )N
compounds. Figure 5 shows the comparison of NTE properties
of Mn3 (Cu0.5 Ge0.5 )N compounds prepared using different
manganese nitrides, i.e. Mn2 N, Mn2 N0.86 and Mn4 N, as
starting materials. It is noted that the NTE start temperature
4
Fast Track Communication
decreases from 365 K to 320 K then to 250 K, the operation
temperature range decreases from 85 K to 80 K and further
to 35 K, while the CNTE increases from −12 × 10−6 K−1
to −16 × 10−6 K−1 and further to −85 × 10−6 K−1 , when
Mn2 N, Mn2 N0.86 and Mn4 N were used as the starting materials,
respectively. The above tendencies indicate that with the
reduction in nitrogen content in the starting manganese
nitride, both the NTE start temperature and the operation
temperature range decrease, whereas the CNTE increases.
The increase in CNTE results from the effects of nitrogen
content reduction on the enhancement of the nearest-neighbour
Mn–Mn exchange interaction. As shown by the antiperovskite
Mn3 CuN-type structure in the inset of figure 5, the lattice
distortion is generated due to the loss of the body-centred
nitrogen atom, hence the exchange interaction of the nearest-
neighbour Mn moments in the  5g antiferromagnetic cubic
structure [9] is strengthened. As a result, the energy for the
antiferromagnetic order–disorder transition is increased at the
transition temperature, which causes the prompt expansion
of lattice volume due to the magnetovolume effect [9].
Consequently, the CNTE value is increased, especially when
there is a relatively lower nitrogen content in the starting
material. According to the analyses, it implies that the NTE
performance of Mn3 (Cu1−x Gex )N compounds can be tailored
by adjusting the nitrogen content in the initial manganese
nitrides.
To summarize, we have prepared the coarse- and ultrafine-
grained Mn3 (Cu1−x Gex )N (x = 0.5) compound bulks both
using Mn2 N0.86 powder as the starting material. In contrast
to Mn2 N that was used as the starting material in previous
studies, the synthesis time of Mn2 N0.86 powder is drastically
reduced from 60 h for Mn2 N [13] to 5 h. Taking advantage
of the sequential processes of crystallization and densification
of amorphous powder during the SPS, the ultrafine-grained
Mn3 (Cu0.5 Ge0.5 )N bulk was fabricated. As compared with
the coarse-grained Mn3 (Cu0.5 Ge0.5 )N compound bulk, the
ultrafine-grained bulk has lower NTE start temperature and
much larger CNTE. We discovered that in the ultrafine-grained
Mn3 (Cu0.5 Ge0.5 )N compound bulk, the NTE performance
takes place in the range of paramagnetism. The reason is
that the magnetostriction effect is greatly enhanced below the
magnetic ordering temperature due to the grain-size effect. It
was found that with the reduction of nitrogen content in the
starting manganese nitride, both the NTE start temperature
and the operation temperature range decrease, whereas the
CNTE increases. The mechanism lies in the effect of nitrogen
content reduction on the enhancement of the nearest-neighbour
Mn–Mn exchange interaction.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant no 50671001 & 50871001), the
Program for New Century Excellent Talents in University
(NCET-06-0182) and the Doctorate Foundation of the Chinese
Education Ministry (20070005010).
J. Phys. D: Appl. Phys. 42 (2009) 122004
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Fast Track Communication
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